The aluminumKand ironLemission bands and the aluminumK&agr;3andK&agr;4satellite lines from a series of aluminum‐iron binary alloys have been studied using 6‐kV electron excitation and a flat crystal x‐ray vacuum spectrometer equipped with a flow proportional counter. It is found that the AlKband energy position and the AlK&agr;4/K&agr;3intensity ratio are both linearly dependent on alloy composition. As the aluminum concentration is lowered, the AlKband intensity maximum shifts to lowery energy and the band becomes more symmetrical in shape. In general, these results are very similar to those obtained previously from the aluminum‐nickel system. The FeLIIIband undergoes very little change in shape but shifts to higher energy as the aluminum‐to‐iron ratio is increased. The spectral changes are interpreted as indicating that the predominately metallic bond in the pure metals acquires a certain amount of covalent‐like character in the alloys with the aluminum atoms behaving as electron donors.